Polysaccharides are semi-flexible polymers composed of sugar residues with a myriad of important functions including structural support and energy storage. The local conformation of such chains is a crucial factor governing their interactions. Traditionally this conformation has only been directly accessible in the solid-state, using crystallographic techniques such as fibre diffraction. Herein it is demonstrated that improvements in the quality of synchrotron-based X-ray scattering data means that conformation-dependent features, the positions of which are related to the linear repeating distance between single saccharide monomers, can now be measured in solution. This technique is expected to be universally applicable for polysaccharides.